CN110665511A - Titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas and preparation method and application thereof - Google Patents
Titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 239000003546 flue gas Substances 0.000 title claims abstract description 48
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 239000012855 volatile organic compound Substances 0.000 title claims abstract description 45
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 33
- 239000011593 sulfur Substances 0.000 title claims abstract description 33
- 239000010936 titanium Substances 0.000 title claims abstract description 33
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 71
- 239000002105 nanoparticle Substances 0.000 claims abstract description 34
- 238000000034 method Methods 0.000 claims abstract description 20
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 17
- 150000003624 transition metals Chemical class 0.000 claims abstract description 13
- 239000002243 precursor Substances 0.000 claims abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000007789 gas Substances 0.000 claims abstract description 7
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 6
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000002390 rotary evaporation Methods 0.000 claims abstract description 4
- 238000004729 solvothermal method Methods 0.000 claims abstract description 4
- 239000010815 organic waste Substances 0.000 claims abstract description 3
- 238000000746 purification Methods 0.000 claims abstract description 3
- 238000003756 stirring Methods 0.000 claims description 36
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000006243 chemical reaction Methods 0.000 claims description 20
- 238000001035 drying Methods 0.000 claims description 15
- 239000000203 mixture Substances 0.000 claims description 14
- 238000002156 mixing Methods 0.000 claims description 12
- 238000001354 calcination Methods 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 238000000227 grinding Methods 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 8
- -1 polytetrafluoroethylene Polymers 0.000 claims description 8
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 8
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 7
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 6
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 6
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 5
- 239000002244 precipitate Substances 0.000 claims description 4
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 2
- 239000007769 metal material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000003915 air pollution Methods 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 230000003647 oxidation Effects 0.000 abstract description 14
- 238000007254 oxidation reaction Methods 0.000 abstract description 14
- 238000006731 degradation reaction Methods 0.000 abstract description 7
- 230000015556 catabolic process Effects 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 239000003245 coal Substances 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 3
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 abstract 2
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 51
- 238000011156 evaluation Methods 0.000 description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000010718 Oxidation Activity Effects 0.000 description 4
- 239000002957 persistent organic pollutant Substances 0.000 description 4
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 229910016553 CuOx Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- DWWOZCUXMGDXEX-UHFFFAOYSA-N [Fe+2].[O-2].[V+5] Chemical compound [Fe+2].[O-2].[V+5] DWWOZCUXMGDXEX-UHFFFAOYSA-N 0.000 description 2
- FDHXJXORQOCVFU-UHFFFAOYSA-N [V].[Cu]=O Chemical compound [V].[Cu]=O FDHXJXORQOCVFU-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- GPRLSGONYQIRFK-UHFFFAOYSA-N hydron Chemical compound [H+] GPRLSGONYQIRFK-UHFFFAOYSA-N 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/847—Vanadium, niobium or tantalum or polonium
- B01J23/8472—Vanadium
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/864—Removing carbon monoxide or hydrocarbons
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- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
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- B01D53/8678—Removing components of undefined structure
- B01D53/8687—Organic components
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/20—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state
- B01J35/23—Catalysts, in general, characterised by their form or physical properties characterised by their non-solid state in a colloidal state
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- B01D2257/00—Components to be removed
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Abstract
The invention discloses a titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas, and a preparation method and application thereof. The method comprises the following steps: dissolving vanadium and a transition metal-based precursor in water, and loading the solution on anatase TiO prepared by a solvothermal method by using a rotary evaporation method2The titanium-based composite catalyst for purifying volatile organic compounds in the high-sulfur coal-fired flue gas is obtained on the nano particles. The catalytic material prepared by the invention has high activity in catalytic oxidation of volatile organic compounds due to the loading of vanadium and transition metal, and particularly shows excellent degradation efficiency of volatile organic compounds and good performance in high sulfur dioxide flue gas atmosphereStability of (2). The prepared catalyst can be widely applied to the fields of purification of flue gas generated in the coal burning process, treatment of high-sulfur organic waste gas and other atmospheric pollution control.
Description
Technical Field
The invention belongs to the technical field of environment function nano materials, and particularly relates to a preparation method of a titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas and application of the titanium-based composite catalyst in atmospheric environmental pollution treatment.
Background
The coal burning process of power plants, coking plants and the like can discharge pollutants with complex types and large total amount, including dust, NOx and SO2And the like, and at the same time, the process also produces Volatile Organic Compounds (VOCs), the harmfulness of which is also not negligible. Volatile organic compounds in the coal-fired flue gas have the characteristics of complex components, low concentration, high toxicity and the like, can cause the generation of ozone and PM2.5, and poses great threats to human health and environment. At present, the research on organic pollutants in the atmosphere at home and abroad mainly focuses on the aspects of industrial source emission, indoor generated volatile organic compounds and the like, and SO in coal-fired flue gas2、NO、NH3The content is very high, the treatment atmosphere is complex, and the existing commercial industrial source volatile organic compound catalytic oxidation technology and material cannot be directly applied. Therefore, the reasonable bifunctional catalyst can be developed to remove volatile organic compounds under the condition of complex coal-fired flue gas, and has very important scientific significance and practical application value.
TiO2The supported transition metal or noble metal catalyst has good reducibility and is suitableIs widely used for catalyzing and oxidizing VOCs. Vanadium oxide has good SO2Tolerance and appropriate amount of surface acidity.
In view of the above, the invention develops a titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas aiming at the problems of catalytic oxidation of VOCs in the coal-fired flue gas, and the titanium-based composite catalyst has good catalytic oxidation activity of VOCs and obvious SO2Tolerance and good stability. The invention provides a new idea and direction for the fields of purification of flue gas generated in the coal burning process, treatment of high-sulfur organic waste gas and other atmospheric pollution control.
Disclosure of Invention
The invention aims to develop a titanium-based composite catalyst which can adapt to complex volatile organic compounds in coal-fired flue gas, and realize excellent activity and obvious SO of the catalyst under the condition of high-sulfur coal-fired flue gas2Tolerance, and provides a simple preparation method of the titanium-based composite catalyst for purifying volatile organic compounds in the high-sulfur coal-fired flue gas and application thereof in atmospheric environmental pollution treatment.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas comprises the steps of dissolving vanadium and a transition metal-based precursor in water, and loading the vanadium and the transition metal-based precursor on anatase TiO2 nano particles prepared by a solvothermal method by using a rotary evaporation method to obtain the titanium-based composite catalyst for purifying the volatile organic compounds in the coal-fired flue gas.
The method comprises the following steps:
(1) preparation of anatase TiO2 nanoparticles:
mixing ethanol and ammonia water to obtain a solution A, mixing tetrabutyl titanate and ethanol to obtain a solution B, simultaneously stirring the solution A and the solution B at room temperature for 10 ~ 30 min, dropwise adding the solution B into the solution A to obtain a solution C, stirring at room temperature, transferring the solution C into a polytetrafluoroethylene reaction kettle inner container, finally placing the polytetrafluoroethylene reaction kettle inner container into a high-pressure reaction kettle, carrying out hydrothermal reaction, naturally cooling, carrying out centrifugal washing on a precipitate by using ethanol, carrying out vacuum drying, and grinding to obtain anatase TiO2 nano-particles, wherein the volume of ethanol in the solution A is 30 ~ 50mL, the volume of ammonia water in the solution A is 1 ~ 3 mL, the volume of tetrabutyl titanate in the solution B is 3 ~ 8 mL, and the volume of ethanol in the solution B is 10 ~ 30 mL;
(2) preparation of anatase TiO2 nanoparticles loaded with vanadium-transition metals:
fully mixing ammonium metavanadate, a transition metal-based precursor and deionized water, placing the mixture in a heat-collecting constant-temperature magnetic stirrer, fully stirring at constant temperature to dissolve the mixture, adding the anatase TiO2 nanoparticles prepared in the step (1) under a stirring state, ultrasonically stirring the mixture in a rotary evaporator until the mixture is dried by distillation, drying, grinding and calcining the mixture to obtain an anatase TiO2 nanoparticle-loaded vanadium-transition metal material, wherein the mass of the anatase TiO2 nanoparticles is 1 ~ 5 g, the addition amount of the ammonium metavanadate accounts for 0.5% ~ 2% of the mass of the anatase TiO2 nanoparticles, the addition amount of the transition metal-based precursor accounts for 1% ~ 30% of the anatase TiO2 nanoparticles, the transition metal-based precursor comprises copper nitrate or iron nitrate, and the volume of the deionized water is 20 ~ 40 mL.
In the method, in the step (1), the stirring time of the solution C is 20 ~ 40 min, and the stirring speed is 400 ~ 500 r/min.
In the method, in the step (1), the hydrothermal reaction temperature is 120 ~ 150 ℃, the hydrothermal reaction pressure is 0.1 ~ 0.3.3 MPa, the reaction time is 10 ~ 15 h, the vacuum drying temperature is 100 ~ 110 ℃, and the drying time is 10 ~ 12 h.
In the method, in the step (1), the rotating speed of the centrifugal washing centrifuge is 6000 ~ 8000 r/min, the centrifugation time is 3 ~ 6 min/time, and the washing times are 3 ~ 5 times.
In the method, in the step (2), the stirring temperature of the heat collection type constant temperature magnetic stirrer is 60 ~ 80 ℃, the stirring time is 20 ~ 40 min, the stirring speed is 400 ~ 500r/min, and the ultrasonic time is 20 ~ 60 min.
In the method, in the step (2), the stirring speed of the rotary evaporator is 120 ~ 150 rpm, the temperature is 50 ~ 60 ℃, the drying temperature is 100 ~ 110 ℃, the drying time is 10 ~ 12 h, the calcining temperature is 400 ~ 500 ℃, the calcining time is 3 ~ 5h, and the heating rate is 2 ~ 5 ℃/min.
In the method, the specific calcining method comprises the steps of heating from room temperature to 280 ~ 320 ℃ at the speed of 2 ~ 4 ℃/min to 280 ~ ℃ at the constant temperature of 280 ~ 320 ℃ for 30 ~ 80 min, heating from 350 ~ 550 ℃ at the speed of 2 ~ 4 ℃/min to 350 ~ ℃ at the constant temperature of 3 ~ 5h, and cooling to room temperature at the speed of 1 ~ 5 ℃/min.
A titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas is applied to the field of degradation of volatile organic pollutants in the atmosphere.
The invention dissolves vanadium and transition metal-based precursor in water, and utilizes a rotary evaporation method to load anatase TiO prepared by a solvothermal method2The titanium-based composite catalyst for purifying volatile organic compounds in the high-sulfur coal-fired flue gas is obtained on the nano particles. The catalyst has high activity and obvious SO2Tolerance, good stability and the like.
Compared with the prior art, the invention has the following advantages:
(1) the preparation method adopted by the invention is simple and feasible, the active components can be regulated and controlled in a larger range, and the vanadium-doped transition metal oxide can be better in anatase TiO2Dispersing on the nano-particle carrier.
(2) The titanium-based composite catalyst prepared by the method is used for purifying volatile organic pollutants in coal-fired flue gas for the first time, and shows excellent catalytic oxidation activity of VOCs and good stability under the condition of high-sulfur coal-fired flue gas. The catalyst can be widely applied to the field of degradation of volatile organic pollutants in the atmosphere.
Drawings
FIG. 1 shows a Ti-based composite catalyst, anatase TiO, for purifying volatile organic compounds in high-sulfur coal-fired flue gas according to the present invention2XRD pattern of nanoparticle powder;
FIG. 2 is an activity evaluation chart of toluene catalytic oxidative degradation of a titanium-based composite catalyst and a commercial catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas according to the present invention under the coal-fired flue gas condition;
FIG. 3 is a 24-hour stability evaluation chart of the catalytic oxidation efficiency of toluene under the coal-fired flue gas condition of the titanium-based composite catalyst and the commercial catalyst for purifying volatile organic compounds in the high-sulfur coal-fired flue gas.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention are not limited thereto, and may be carried out with reference to conventional techniques for process parameters not particularly noted.
Example 1
(1) Anatase TiO2Preparing nano particles:
mixing 40 mL of ethanol and 2 mL of ammonia water to obtain a solution A, mixing 50mL of tetrabutyl titanate and 10 mL of ethanol to obtain a solution B, simultaneously stirring the solution A and the solution B at room temperature for 20 min, then dropwise adding the solution B into the solution A to obtain a solution C, stirring at room temperature for 30 min, transferring the solution C into a polytetrafluoroethylene reaction kettle inner container, finally placing the polytetrafluoroethylene reaction kettle inner container into a high-pressure reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 12 h, naturally cooling, centrifugally washing the precipitate for 3 times by using ethanol at 6500 r/min, transferring into a 105 ℃ vacuum drying oven for drying for 12 h, and grinding to obtain anatase TiO2A nanoparticle;
(2) anatase TiO2Preparing the nano-particle loaded vanadium-copper oxide:
fully mixing 0.046 g of ammonium metavanadate, 0.296 g of copper nitrate and 20 mL of deionized water, putting the mixture into a heat-collecting constant-temperature magnetic stirrer, fully stirring the mixture for 30 min at the temperature of 70 ℃ and the stirring speed of 450 r/min to dissolve the mixture, and adding the anatase TiO prepared in the step (1) into the mixture under the stirring state2Subjecting the nanoparticles to ultrasonic treatment for 30 min, transferring into a rotary evaporator, stirring at 60 deg.C and stirring rate of 150 rpm, evaporating, transferring into a 105 deg.C blast drying oven, drying for 12 h, grinding, calcining at high temperature in a muffle furnace, heating at 4.5 deg.C/min from room temperature to 300 deg.C, maintaining at 300 deg.C for 1h, heating at 3 deg.C/min from 300 deg.C to 450 deg.C, maintaining at 450 deg.C for 4h, and heating at 2 deg.C/mi for 4hThe n rate is reduced to room temperature to obtain anatase TiO2The nanoparticles support a vanadium-copper oxide material.
As can be seen from the X-ray diffraction pattern (FIG. 1) of the catalyst, anatase TiO was successfully produced2The supported vanadium-doped copper oxide catalyst has high crystallinity.
Example 2
(1) Anatase TiO2Preparing nano particles:
mixing 50mL of ethanol and 2 mL of ammonia water to obtain a solution A, mixing 50mL of tetrabutyl titanate and 10 mL of ethanol to obtain a solution B, simultaneously stirring the solution A and the solution B at room temperature for 30 min, then dropwise adding the solution B into the solution A to obtain a solution C, stirring at room temperature for 30 min, transferring the solution C into a polytetrafluoroethylene reaction kettle inner container, finally placing the polytetrafluoroethylene reaction kettle inner container into a high-pressure reaction kettle, carrying out hydrothermal reaction at 150 ℃ for 12 h, naturally cooling, centrifugally washing the precipitate for 2 times by using ethanol at 8000 r/min, transferring into a vacuum drying oven at 110 ℃ for drying for 12 h, and grinding to obtain anatase TiO2A nanoparticle;
(2) anatase TiO2Preparing the nanoparticle-loaded vanadium-iron oxide:
fully mixing 0.046 g of ammonium metavanadate, 0.724 g of ferric nitrate and 20 mL of deionized water, putting the mixture into a heat-collecting constant-temperature magnetic stirrer, fully stirring the mixture for 30 min at the temperature of 80 ℃ and the stirring speed of 450 r/min to dissolve the mixture, and adding the anatase TiO prepared in the step (1) in a stirring state2Subjecting the nanoparticles to ultrasonic treatment for 30 min, transferring to a rotary evaporator, stirring at 60 deg.C and stirring rate of 150 rpm, evaporating, transferring to a 110 deg.C blast drying oven, drying for 12 h, grinding, calcining at high temperature in a muffle furnace, heating at 3 deg.C/min from room temperature to 300 deg.C, maintaining at 300 deg.C for 0.5h, heating at 3 deg.C/min from 300 deg.C to 450 deg.C, maintaining at 450 deg.C for 4h, and cooling at 3 deg.C/min to room temperature to obtain anatase TiO2The nanoparticles support a vanadium-iron oxide material.
Example 3
Evaluation of catalytic oxidation activity of VOCs: miningWith toluene (C)7H8) The catalytic oxidation toluene degradation reaction is carried out on a self-made reactor under the test conditions that the toluene concentration is 50ppm, the catalyst dosage is 100 mg, the reaction temperature is 150 ℃, the temperature is ~ 390 ℃, the reaction flow rate is 200 mL/min, and the space velocity is 120000 h-1The reaction atmosphere is simulated coal-fired flue gas, wherein NH3 Concentration 50 ~ 500 ppm (50 ppm in this example), NO concentration 50 ~ 500 ppm (50 ppm in this example), SO2The concentration was 50 ~ 1500 ppm (1000 ppm in this example), 5 vol% O2，N2Is a balance gas; the concentration of toluene was measured using a flame detector with hydrogen ion (FID) and a gas chromatograph connected to a nickel reformer. FIG. 2 is VOx-CuOx/TiO2The activity evaluation chart of the catalyst and the commercial catalyst (Shandong Yuhai environmental protection science and technology Co., Ltd.) for the catalytic oxidation degradation of toluene shows that the reaction temperature (T) is the reaction temperature (T) when the toluene catalytic oxidation removal rate of the titanium-based composite catalyst for purifying volatile organic compounds in the high-sulfur coal-fired flue gas reaches 90 percent90) Is 318 ℃; t for catalytic oxidation of toluene by commercial catalyst under coal-fired flue gas condition90Above 365 ℃. The results fully show that the titanium-based composite catalyst for purifying volatile organic compounds in the high-sulfur coal-fired flue gas shows excellent catalytic oxidation activity of VOCs in the high-sulfur flue gas atmosphere.
Example 4
Evaluation of catalytic oxidation stability of VOCs: with toluene (C)7H8) As a probe molecule, catalytic oxidation stability of the catalyst to toluene at a fixed temperature was investigated. The degradation reaction of the catalytic oxidation toluene is carried out on a self-made reactor, and the test conditions are as follows: the concentration of toluene is 50ppm, the dosage of the catalyst is 100 mg, the reaction temperature is 350 ℃, the reaction flow rate is 200 mL/min, and the space velocity is 120000 h-1The reaction atmosphere is simulated coal-fired flue gas, wherein NH3 Concentration 50 ~ 500 ppm (50 ppm in this example), NO concentration 50 ~ 500 ppm (50 ppm in this example), SO2The concentration was 50 ~ 1500 ppm (1000 ppm in this example), 5 vol% O2，N2Is a balance gas; the concentration of toluene was measured using a flame detector with hydrogen ion (FID) and a gas chromatograph connected to a nickel reformer. FIG. 3 is VOx-CuOx/TiO2The catalyst and the commercial catalyst have a stability evaluation chart of toluene catalytic oxidation degradation, and the result shows that the toluene catalytic oxidation removal rate of the titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas is still kept above 90% after 24 hours, while the toluene catalytic oxidation removal rate of the commercial catalyst is only 30% after 24 hours under the coal-fired flue gas condition. The results show that the titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas shows significant SO2Tolerance and good stability.
The above examples are merely illustrative of the technical solutions of the present invention and not restrictive, and it will be understood by those of ordinary skill in the art that various changes in the details or forms thereof may be made without departing from the spirit and scope of the present invention as defined by the claims.
Claims (10)
1. A preparation method of a titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas is characterized in that vanadium and a transition metal-based precursor are dissolved in water, and an anatase TiO prepared by a rotary evaporation method and loaded on a solvothermal method is utilized2And (4) obtaining the titanium-based composite catalyst for purifying volatile organic compounds in the coal-fired flue gas on the nano particles.
2. The preparation method of the titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas according to claim 1, characterized by comprising the following steps:
anatase TiO2Preparing nano particles:
mixing ethanol and ammonia water to obtain solution A, mixing tetrabutyl titanate and ethanol to obtain solution B, stirring solution A and solution B at room temperature for 10 ~ 30 min, adding solution B into solution A dropwise to obtain solution C, stirring at room temperature, transferring to inner container of polytetrafluoroethylene reaction kettle, and adding polytetrafluoroethylene into the inner containerPutting the inner container of the reaction kettle into a high-pressure reaction kettle, carrying out hydrothermal reaction, naturally cooling, centrifugally washing the precipitate with ethanol, drying in vacuum, and grinding to obtain anatase TiO2The volume of ethanol in the solution A is 30 ~ 50mL, the volume of ammonia water in the solution A is 1 ~ 3 mL, the volume of tetrabutyl titanate in the solution B is 3 ~ 8 mL, and the volume of ethanol in the solution B is 10 ~ 30 mL;
anatase TiO2Preparing the nano-particle loaded vanadium-transition metal:
fully mixing ammonium metavanadate, a transition metal-based precursor and deionized water, placing the mixture in a heat-collecting constant-temperature magnetic stirrer, fully stirring at constant temperature to dissolve the mixture, and adding the anatase TiO prepared in the step (1) in a stirring state2Transferring the nano particles to a rotary evaporator after ultrasonic treatment, violently stirring the nano particles until the nano particles are evaporated to dryness, and drying, grinding and calcining the nano particles to obtain anatase TiO2The nanoparticles support a vanadium-transition metal material; the anatase TiO2The mass of the nano particles is 1 ~ 5 g, and the addition amount of the ammonium metavanadate accounts for the anatase TiO2~ 2% of the mass of the nano particles, wherein the addition amount of the transition metal-based precursor accounts for 0.5% of that of anatase TiO21% ~ 30% of nanoparticles, the transition metal-based precursor comprising copper nitrate or iron nitrate, the volume of deionized water being 20 ~ 40 mL.
3. The preparation method of the titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas as claimed in claim 2, wherein in the step (1), the stirring time of the solution C is 20 ~ 40 min, and the stirring speed is 400 ~ 500 r/min.
4. The preparation method of the titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas as claimed in claim 2, wherein in the step (1), the hydrothermal reaction temperature is 120 ~ 150 ℃, the hydrothermal reaction pressure is 0.1 ~ 0.3.3 MPa, the reaction time is 10 ~ 15 h, the vacuum drying temperature is 100 ~ 110 ℃, and the drying time is 10 ~ 12 h.
5. The preparation method of the titanium-based composite catalyst for purifying volatile organic compounds in the high-sulfur coal-fired flue gas as claimed in claim 2, wherein in the step (1), the rotation speed of the centrifugal washing centrifuge is 6000 ~ 8000 r/min, the centrifugation time is 3 ~ 6 min/time, and the washing times are 3 ~ 5 times.
6. The preparation method of the titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas as claimed in claim 2, wherein in the step (2), the stirring temperature of the heat-collecting type constant-temperature magnetic stirrer is 60 ~ 80 ℃, the stirring time is 20 ~ 40 min, the stirring speed is 400 ~ 500r/min, and the ultrasonic time is 20 ~ 60 min.
7. The preparation method of the titanium-based composite catalyst for purifying volatile organic compounds in the high-sulfur coal-fired flue gas as claimed in claim 2, wherein in the step (2), the stirring speed of the rotary evaporator is 120 ~ 150 rpm, the temperature is 50 ~ 60 ℃, the drying temperature is 100 ~ 110 ℃, the drying time is 10 ~ 12 h, the calcining temperature is 400 ~ 500 ℃, the calcining time is 3 ~ 5h, and the heating rate is 2 ~ 5 ℃/min.
8. The preparation method of the titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas as claimed in claim 6, wherein the calcination is carried out by the steps of raising the temperature from room temperature to 280 ~ 320 ℃ at a speed of 2 ~ 4 ℃/min, maintaining the temperature at 280 ~ 320 ℃ for 30 ~ 80 min, raising the temperature at 2 ~ 4 ℃/min to 350 ~ 550 ℃ at 3 ~ 5h, and finally lowering the temperature to room temperature at a speed of 1 ~ 5 ℃/min.
9. The titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas, which is prepared by the preparation method of any one of claims 1 ~ 8.
10. The titanium-based composite catalyst for purifying volatile organic compounds in high-sulfur coal-fired flue gas as claimed in claim 9 is applied to the fields of air pollution control such as flue gas purification and high-sulfur organic waste gas treatment in the coal-fired process.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083280A (en) * | 2021-04-22 | 2021-07-09 | 中国科学院过程工程研究所 | High-load vanadium-titanium oxide catalyst for catalytic oxidation of VOCs (volatile organic compounds), and preparation method and application thereof |
Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113018A (en) * | 2006-07-26 | 2008-01-30 | 黑龙江大学 | Preparation method of highlight catalytic active titanium oxide |
| JP2009013038A (en) * | 2007-07-09 | 2009-01-22 | National Institute Of Advanced Industrial & Technology | Super-hydrophilic/hydrophobic patternized surface, anatase tio2 crystal pattern and their preparation methods |
| CN101607203A (en) * | 2009-07-16 | 2009-12-23 | 浙江大学 | Be used to remove the Catalysts and its preparation method of dioxin-type halogenated aromatic compounds |
| CN103301846A (en) * | 2013-07-11 | 2013-09-18 | 中南大学 | InVO4.Cu2O.TiO2 ternary complex and preparation method and application thereof |
| CN103608090A (en) * | 2011-05-11 | 2014-02-26 | 莎哈利本颜料有限公司 | Raw materials for vanadium-free or vanadium-reduced DeNOx catalysts, and method for producing same |
| CN107376895A (en) * | 2017-07-04 | 2017-11-24 | 清华大学 | A kind of Collaborative Control NOxWith the preparation method and applications of CVOCs trifolium-shaped catalyst |
| CN108126685A (en) * | 2017-11-14 | 2018-06-08 | 浙江大学 | Two-part catalyst of catalytic degradation VOCs containing chlorine and its preparation method and application |
| CN110026170A (en) * | 2019-05-23 | 2019-07-19 | 乐山师范学院 | A kind of TiO of photocatalytic degradation rhodamine B2Photochemical catalyst and preparation method thereof |
| CN110090645A (en) * | 2019-05-10 | 2019-08-06 | 天河（保定）环境工程有限公司 | A kind of combined denitration takes off dioxin catalyst and preparation method thereof |
| CN110227433A (en) * | 2019-06-26 | 2019-09-13 | 浙江大学 | A kind of Detitanium-ore-type TiO2The preparation method of crystal face hetero-junctions |
-
2019
- 2019-09-27 CN CN201910921283.6A patent/CN110665511B/en active Active
Patent Citations (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101113018A (en) * | 2006-07-26 | 2008-01-30 | 黑龙江大学 | Preparation method of highlight catalytic active titanium oxide |
| JP2009013038A (en) * | 2007-07-09 | 2009-01-22 | National Institute Of Advanced Industrial & Technology | Super-hydrophilic/hydrophobic patternized surface, anatase tio2 crystal pattern and their preparation methods |
| CN101607203A (en) * | 2009-07-16 | 2009-12-23 | 浙江大学 | Be used to remove the Catalysts and its preparation method of dioxin-type halogenated aromatic compounds |
| CN103608090A (en) * | 2011-05-11 | 2014-02-26 | 莎哈利本颜料有限公司 | Raw materials for vanadium-free or vanadium-reduced DeNOx catalysts, and method for producing same |
| CN103301846A (en) * | 2013-07-11 | 2013-09-18 | 中南大学 | InVO4.Cu2O.TiO2 ternary complex and preparation method and application thereof |
| CN107376895A (en) * | 2017-07-04 | 2017-11-24 | 清华大学 | A kind of Collaborative Control NOxWith the preparation method and applications of CVOCs trifolium-shaped catalyst |
| CN108126685A (en) * | 2017-11-14 | 2018-06-08 | 浙江大学 | Two-part catalyst of catalytic degradation VOCs containing chlorine and its preparation method and application |
| CN110090645A (en) * | 2019-05-10 | 2019-08-06 | 天河（保定）环境工程有限公司 | A kind of combined denitration takes off dioxin catalyst and preparation method thereof |
| CN110026170A (en) * | 2019-05-23 | 2019-07-19 | 乐山师范学院 | A kind of TiO of photocatalytic degradation rhodamine B2Photochemical catalyst and preparation method thereof |
| CN110227433A (en) * | 2019-06-26 | 2019-09-13 | 浙江大学 | A kind of Detitanium-ore-type TiO2The preparation method of crystal face hetero-junctions |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113083280A (en) * | 2021-04-22 | 2021-07-09 | 中国科学院过程工程研究所 | High-load vanadium-titanium oxide catalyst for catalytic oxidation of VOCs (volatile organic compounds), and preparation method and application thereof |
| CN113083280B (en) * | 2021-04-22 | 2022-05-13 | 中国科学院过程工程研究所 | High-load vanadium-titanium oxide catalyst for catalytic oxidation of VOCs (volatile organic compounds), and preparation method and application thereof |
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